CN101081741A - Preparation method of A1-A1N-ZrO2 ceramic material - Google Patents
Preparation method of A1-A1N-ZrO2 ceramic material Download PDFInfo
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- CN101081741A CN101081741A CN 200710084521 CN200710084521A CN101081741A CN 101081741 A CN101081741 A CN 101081741A CN 200710084521 CN200710084521 CN 200710084521 CN 200710084521 A CN200710084521 A CN 200710084521A CN 101081741 A CN101081741 A CN 101081741A
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Abstract
The present invention is process of preparing Al-AlN-ZrO2 ceramic material, and belongs to the field of polyphase ceramic-based cermet material technology. The process includes the following steps: wet mixing metal Al, partially stable ZrO2, pre-composed AlN, sintering assistant and anhydrous alcohol through stirring for 30 min; forming the mixture at pressure of 20-100 MPa; high temperature nitriding and sintering at 1400-1600 deg.c for 2-6 hr; and oxidizing the surface of the sintered material at 960 deg.c for 30 min. The prepared polyphase Al-AlN-ZrO2 ceramic material has high heat shock resistance.
Description
[technical field]
The invention belongs to the stupalith field, be specifically related to preparation technology's method of highly heatproof and shockproof Zirconia ceramic matrix multiphase metal ceramics structured material.
[background technology]
To such an extent as at present the molten steel tundish metering nozzle material in the metallurgical industry billet continuous casting system exists and is subjected to that the transient heat shock action takes place very easily that the thermal shock cracking peels off, aperture, the mouth of a river enlarges and cause watering the practical problems that badly bleeding damage continuous casting key equipment crystallizer is interrupted even causes in the steel operation, and is never solved well.
The nineties in last century, the Lanxide company of the U.S. once developed AlN-Al-MgO nitriding treatment material, the nineties in last century, the Lanxide company of the U.S. develops the type material of a kind of being called as " DIMOX ", its manufacturing process is: magnesite clinker or spinel particle are placed in the special refractory materials container, go in the above-mentioned particle gap being added to after the fusion of metal aluminum or aluminum alloy then and carry out nitriding treatment simultaneously, the major ingredient that finally obtains material is MgO (or MA)-AlN-Al.This material thermal shock resistance and good, the more traditional Al of erosion-resisting characteristics
2O
3-ZrO
2-C material lifetime improves 2-3 doubly.Its technical thought provides the research approach for the improvement of zirconia metering nozzle material.
" metallic aluminium-aluminium nitride combined corundum (Al-AlN-Al has been studied in Institutes Of Technology Of Hebei's Materials Academy and the cooperative development of Tang Gang refractory materials company limited
2O
3) composite diphase material, its manufacturing process is to adopt tabular Al
2O
3Particle, α-Al
2O
3The fine powder of fine powder, metal A l and fiber are raw material, and the base substrate after the moulding carries out nitridation sintered under nitrogen environment, 1100 ℃ of nitridation sintered temperature, and the major ingredient that finally obtains material is Al-AlN-Al
2O
3The Al-AlN-Al that is developed
2O
3It is existing Al work-ing life that slide plate waters steel
2O
32 times of-C matter slide plate.But Al
2O
3Compare ZrO
2High temperature resistant and erosion-resisting characteristics is low, Al-AlN-Al
2O
3Composite diphase material is difficult to the use properties requirement of competent metering nozzle.
Metal A l and AlN are applied to the rare at present report of research of refractory materials aspect, but clear metal A l of the example table of above-mentioned domestic and international two successful Application and AlN can cooperate the manufacturing high temperature resistant structure ceramics with resistant to elevated temperatures main raw material.With metal A l and AlN and resistant to elevated temperatures ZrO
2Cooperate, at metal A l, AlN and ZrO
2The rerum natura characteristics, adopt wet-mixed, pressure forming, reaction sintering prepares Al-AlN in conjunction with ZrO under condition of nitrogen gas
2Composite diphase material, this material can be competent at the working conditions of ferrous metallurgy continuous casting system tundish metering nozzle, be expected to become the metallurgical continuous casting metering nozzle more novel material.To this composite diphase material preparation technology's research, still belong to blank at home at present.
[summary of the invention]
The objective of the invention is provides a kind of preparation method of novel composite diphase material in order to overcome deficiency of the prior art.
Technical scheme of the present invention:
A kind of metal A l-AlN is characterized in that may further comprise the steps in conjunction with the preparation method of zirconium white composite diphase material: admixtion wet-mixed, forming materials, high temperature sintering and material surface oxide treatment.
Wet-mixed technology is with metallic aluminium, PSZ ZrO
2, synthetic AlN, sintering agent are prepared burden by weight percentage in advance: metal A l 4-10%, partially stabilized ZrO
285-92%, AlN 3-6%, sintering agent 0.5-2%, after batching and dried the mixing, the dehydrated alcohol that adds q.s forms the slurry with good fluidity, then slurry is carried out wet method and stirs 30 minutes, obtains the powder for moulding after the slurry removal ethanol seasoning after wet method is stirred.
Obtaining for an amount of wedding agent of adding behind the powder of moulding, and mixing, obtaining the blank of forming materials.
Used wedding agent comprises: resol, PVA, honey or thicken pulp waste liquid.
Method of forming materials is to adopt hydropress or friction press to carry out the body of material moulding, and moulding pressure is 20MPa-100Mpa.
Material agglomerating atmosphere is nitrogen atmosphere.
Material agglomerating temperature is 1400-1600 ℃, and soaking time is 2h-6h.
When adopting PVA, honey or thicken pulp waste liquid, need carry out hydrophobic or the processing of anti-aquation to metal A l and AlN.
Material after nitridation sintered need carry out oxide treatment, and the temperature of oxide treatment is 960 ℃, constant temperature 30 minutes.
The present invention according to metal A l-AlN in conjunction with ZrO
2The requirement of the microstructure of composite diphase material, nitridation sintered reaction and use properties, carry out the processing method of wet-mixed after the mixing employing dry mixed to admixtion again, make the each component of batching can full and uniformization, guarantee that the nitrogenizing reaction to base substrate inside can form the weave construction with functionally gradient to material from the base substrate top layer when nitridation sintered.Admixtion is adopted wet-mixed technology, because the homogenizing degree height of each batching component, the thing of the material internal after nitridation sintered distributes mutually and helps improving the anti-molten steel erosion performance of high temperature of material with the homogenizing of weave construction, and distribute mutually homogenizing with weave construction of material internal thing also helps the thermal stresses of experience thermal shock process when reducing material and using, and improves the thermal shock resistance of material.
At the sintering character requirement of zirconia material, determine 1400-1600 ℃ of sintering temperature as this composite diphase material, in order to guarantee the abundant sintering of composite diphase material, soaking time is defined as 2-6 hour.
The present invention is according to zirconium white ZrO
2, aluminium nitride AlN and the Plastic Deformation rerum natura mutually and the use properties requirement of material, particularly at the sintering character requirement of zirconia material, determine the 1400-1600 ℃ of sintering temperature as this composite diphase material, in order to guarantee the abundant sintering of composite diphase material, soaking time is defined as 2-6 hour.
The sintering nitrogen atmosphere of composite diphase material, nitrogen flow is controlled to be during experiment condition: room temperature～400 ℃ are 0.04L/min, and 400～800 ℃ is 0.08L/min, and 800～1600 ℃ is 0.12～0.14L/min.The nitrogen flow of Industrial processes should and need agglomerating base substrate volume (weight) to decide according to the kiln volume.
Because of Al or AlN are easy to aquation and the volumetric expansion effect are arranged, when blank wedding agent as claimed in claim 4 adopts the PVA aqueous solution, honey diluent, thicken pulp waste liquid etc., need carry out hydrophobic or the processing of anti-aquation to metal A l or AlN, to guarantee that Al or AlN energy stable existence is in base substrate.
Need carry out 30 minutes oxide treatment of 960 ℃ of constant temperature to the material after nitridation sintered.The purpose of the material after nitridation sintered being carried out oxide treatment is to make the Al of bill of material surface layer or AlN be converted into the stable material A1 that is difficult for aquation
2O
3, can avoid material in the transportation use, aquation to take place, the more important thing is that Al or AlN are oxidized to Al
2O
3The volume effect of following has the effect of compact material upper layer, so can improve the anti-molten steel erosive of the high temperature ability of material.
The technical requirements of the raw material that the embodiment of the invention is used is as shown in table 1, and the Al-AlN of preparation is in conjunction with ZrO
2The key technical indexes that composite diphase material reaches is shown in table 2.The increasing weight of oxidation of ANZ sample and the relation of temperature are shown in accompanying drawing 1, before the oxidation of ANZ sample and the SEM microstructure after the oxidation be shown in accompanying drawing 2, accompanying drawing 3.
By the composite diphase material technical indicator of table 2 as can be known, metal A l-AlN is in conjunction with ZrO
2Composite diphase material has good thermal shock resistance, and the alternately thermal shock number of times of 1100 ℃-room temperature of experience water-cooled reaches more than 8 times and do not damage, and contrast experiment's the same thermal shock process of zirconia material sample experience only 2 times fracture damage just takes place.Therefore, adopting the present invention is that the Al-AlN of high thermal shock stability is in conjunction with ZrO
2The preparation method of composite diphase material.
The requirement of table 1 material technology
| Starting material | Physical chemistry is formed | Specification |
| PSZ metallic aluminium Al Strontium carbonate powder titanium dioxide aluminium nitride | ZrO 2≥96％ Al≥98％ SrCO 3≥99％ TiO 2≥99％ AlN＞90％ | ＜0.04mm ＜0.04mm ＜0.15mm ＜0.15mm ＜0.04mm |
Table 2 composite diphase material the key technical indexes
| Material property | Technical indicator |
| Volume density void content refractoriness folding strength heat-shock resistance (1l00 ℃-water-cooled, number of times) | ≥3.54g/cm 3≤ 12.4% 〉=1800 ℃ 〉=25MPa 〉=8 times |
[description of drawings]
Fig. 1 is the increasing weight of oxidation of ANZ sample of the present invention and the relation of temperature
Fig. 2 is a SEM microstructure before the ANZ sample of the present invention oxidation
Fig. 3 is an ANZ sample zone of oxidation SEM microstructure of the present invention
[embodiment]
Embodiment 1
Batching is formed: the zirconium white 88% of particle diameter＜0.04 mm; The metal A l 4% of particle diameter＜0.04mm; The AlN 6% of particle diameter＜0.04mm; The SrCO of particle diameter＜0.01mm
32%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and SrCO in advance
3Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 50MPa; Sample material adopts nitriding atmosphere to burn till, and nitrogen flow is controlled to be: room temperature～400 ℃ are 0.04L/min, and 400～800 ℃ is 0.08L/min, and 800～1600 ℃ is 0.12～0.14L/min, and the nitrogenize firing temperature is 1600 ℃, and soaking time is 4h.
The intensity of burning the back sample is 69.34MPa, the intensity 16.17MPa after the thermal shock, the intensity 9.53MPa after three thermal shocks, the intensity 5.13MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is that sample is heated to 1100 ℃ of insulations 30 minutes, takes out and carries out 20 ℃ of water-cooleds of room temperature, repeats repeatedly to carry out.
Embodiment 2
Batching is formed: the zirconium white 87% of particle diameter＜0.04mm, the metal A l 8% of particle diameter＜0.04mm, the AlN 3% of particle diameter＜0.04mm, the TiO of particle diameter＜0.01mm
22%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and TiO in advance
2Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 50MPa; Sample material adopts nitriding atmosphere to burn till, and nitrogen flow is controlled to be: room temperature～400 ℃ are 0.04L/min, and 400～800 ℃ is 0.08L/min, and 800～1500 ℃ is 0.12～0.14L/min, and the nitrogenize firing temperature is 1550 ℃, and soaking time is 4h.
The intensity of burning the back sample is 44.21MPa, the intensity 9.15MPa after the thermal shock, the intensity 6.65MPa after three thermal shocks, the intensity 3.80MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is with embodiment 1.
Embodiment 3
Batching is formed: the zirconium white 86% of particle diameter＜0.04mm; The metal A l 10% of particle diameter＜0.04mm.The AlN 3% of particle diameter＜0.04mm, the SrCO of particle diameter＜0.01mm
31%.
Earlier with metal A l, partially stabilized ZrO
2, synthetic AlN and SrCO in advance
3Prepare burden and dried mixing 1 minute; Add dehydrated alcohol then and make it to form the slurry with flowability, wet method stirred 30 minutes; Slurries filtration after wet method stirred removed behind the ethanol seasoning 2 hours; Adopt pressing machine to carry out the sample moulding, moulding pressure is 50MPa; Sample material adopts nitriding atmosphere to burn till, and nitrogen flow is controlled to be: room temperature～400 ℃ are 0.04L/min, and 400～800 ℃ is 0.08L/min, and 800～1500 ℃ is 0.12～0.14L/min, and the nitrogenize firing temperature is 1450 ℃, and soaking time is 4h.
The intensity of burning the back sample is 28.81MPa, the intensity 6.97MPa after the thermal shock, the intensity 3.82MPa after three thermal shocks, the intensity 2.03MPa after five thermal shocks.Contrast experiment's zirconia material sample only experiences 2 thermal shocks fracture damage just takes place.
The thermal shock test condition is with embodiment 1.
Claims (9)
1, a kind of metal A l-AlN is characterized in that may further comprise the steps in conjunction with the preparation method of zirconium white composite diphase material: admixtion wet-mixed, forming materials, high temperature sintering and material surface oxide treatment.
2, the preparation method of composite diphase material as claimed in claim 1 is characterized in that wet-mixed technology is with metallic aluminium, PSZ ZrO
2, synthetic AlN, sintering agent are prepared burden by weight percentage in advance: metal A l 4-10%, partially stabilized ZrO
285-92%, AlN 3-6%, sintering agent 0.5-2%, after batching and dried the mixing, the dehydrated alcohol that adds q.s forms the slurry with good fluidity, then slurry is carried out wet method and stirs 30 minutes, obtains the powder for moulding after the slurry removal ethanol seasoning after wet method is stirred.
3, the preparation method of composite diphase material as claimed in claim 2 is characterized in that obtaining for an amount of wedding agent of adding behind the powder of moulding, and mixes, and obtains the blank of forming materials.
4, wedding agent as claimed in claim 3 is characterized in that used wedding agent comprises: resol, PVA, honey or thicken pulp waste liquid.
5, the preparation method of composite diphase material as claimed in claim 1 is characterized in that method of forming materials is to adopt hydropress or friction press to carry out the body of material moulding, and moulding pressure is 20MPa-100Mpa.
6, the preparation method of composite diphase material as claimed in claim 1 is characterized in that material agglomerating atmosphere is nitrogen atmosphere.
7, the preparation method of composite diphase material as claimed in claim 1 is characterized in that material agglomerating temperature is 1400-1600 ℃, and soaking time is 2h-6h.
8, blank wedding agent as claimed in claim 4 when it is characterized in that adopting PVA, honey or thicken pulp waste liquid, need carry out hydrophobic or the processing of anti-aquation to metal A l and AlN.
9, the preparation method of composite diphase material as claimed in claim 1 is characterized in that the material after nitridation sintered need carry out oxide treatment, and the temperature of oxide treatment is 960 ℃, constant temperature 30 minutes.
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|---|---|---|---|
| CNB200710084521XA CN100450971C (en) | 2007-02-12 | 2007-02-12 | Preparation method of A1-A1N-ZrO2 ceramic material |
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|---|---|---|---|
| CNB200710084521XA CN100450971C (en) | 2007-02-12 | 2007-02-12 | Preparation method of A1-A1N-ZrO2 ceramic material |
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| CN100450971C CN100450971C (en) | 2009-01-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481246B (en) * | 2009-02-24 | 2012-08-01 | 河北理工大学 | Preparation of ZrO2-Al2TiO5-MgO composite nano powder |
| CN103787655A (en) * | 2012-10-29 | 2014-05-14 | 河北联合大学 | Method for preparing ZrN-Al2O3-ZrO2 multiphase ceramic material by Al-ZrO2-N2 reactive sintering |
| CN103787654A (en) * | 2012-10-29 | 2014-05-14 | 河北联合大学 | Method for preparing ZrN-Al2O3-ZrO2 multiphase ceramic material by aluminum nitride-zirconium dioxide reactive sintering |
| CN104193361A (en) * | 2014-08-15 | 2014-12-10 | 郑州大学 | Preparation process of ZrO2-AlN-C mosaic ring |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296932A (en) * | 2000-12-08 | 2001-05-30 | 黑龙江省锐克复合材料有限公司 | Process for preparing aluminium nitride ceramic powder |
| CN1216010C (en) * | 2002-01-22 | 2005-08-24 | 北京科技大学 | Process for synthesizing superfine aluminium nitride powder and aluminium based heterogeneous ceramic powder by SHS method |
| KR100721780B1 (en) * | 2005-05-30 | 2007-05-25 | 주식회사 다이너머트리얼스 | Method for manufacturing high strength ultra-fine/nano-structured Al/AlN or Al alloy/AlN composite materials |
-
2007
- 2007-02-12 CN CNB200710084521XA patent/CN100450971C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481246B (en) * | 2009-02-24 | 2012-08-01 | 河北理工大学 | Preparation of ZrO2-Al2TiO5-MgO composite nano powder |
| CN103787655A (en) * | 2012-10-29 | 2014-05-14 | 河北联合大学 | Method for preparing ZrN-Al2O3-ZrO2 multiphase ceramic material by Al-ZrO2-N2 reactive sintering |
| CN103787654A (en) * | 2012-10-29 | 2014-05-14 | 河北联合大学 | Method for preparing ZrN-Al2O3-ZrO2 multiphase ceramic material by aluminum nitride-zirconium dioxide reactive sintering |
| CN104193361A (en) * | 2014-08-15 | 2014-12-10 | 郑州大学 | Preparation process of ZrO2-AlN-C mosaic ring |
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|---|---|
| CN100450971C (en) | 2009-01-14 |
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Granted publication date: 20090114 Termination date: 20120212 |